Abstract: A method has been investigated which allows calculations from the X-ray fluorescence spectra of the absorption coefficients at any energy for any sample, without any additional measurement. Use is made of the ratio of the characteristic X-ray signals from a Zr wire positioned in front of the sample and from a Pd foil placed behind the sample, both in a fixed geometry. From the experimentally measured absorption coefficient at the Pd L energy (2.9 keV), the coefficients for higher energies are calculated. By the use of an iterative computer routine in which corrections for the enhancement of the Pd foil by the sample are also included, an accuracy of 2% or better on the absorption coefficient determination can be reached for homogenous samples in one measurement. Grain-size and heterogeneity effects induce inaccuracies on the absorption coefficient determinations which might well reach 20% for particulate samples like intermediate thickness deposits of geological materials. This approach thus has the same limitations as the classical transmission method for such heterogeneous samples.